Abstract The Direct Reduction (DR) process has been growing worldwide, and there are strong context suggestions that it will grow even more. One of these factors is the environmental pressure that occurs worldwide, and there are already projects to migrate Blast Furnace route steel plants to the Direct Reduction (DR) route, due to its smaller carbon footprint. Considering the importance of this process and the challenges of carrying out experimental tests on a pilot scale, an adequate way to evaluate the process and its impacts is through numerical simulations. There are different techniques applied to models that describe the counter-current reactor in the DR process, but none of them account for the clustering phenomenon. Clustering occurs because of the sintering of the metallic iron on the surface of the pellets in such a way that they attach to each other, forming clusters that hinder the gas flow through the shaft. The present study attempted to adapt a numerical model of a DR process to account for the effect of the cluster formation. Some clustering index equations from literature and some developed as part of this study were used and tested in the model, as a function of temperature, by varying the solid volume fraction in the control unit. The equation that resulted in the adjusted output closest to the current empirical value was implemented in the model and proved to be successful.

Abstract Despite the high potential of the freeze-casting technique for production of porous inorganic substrates, there is a lack of studies on tubular geometries and their mechanical behavior under different pressure scenarios. In this work, the mechanical behavior of tubular freeze-cast alumina substrates was assessed by mathematical models from experimental O-ring tests. The stress distributions revealed a concentration of tensile stresses (within 0.2-25.0 MPa) on the plane of the load, causing brittle fracture. Furthermore, the results confirmed that the honeycomb model for brittle material adequately predicted the mechanical strength of the tubular freeze-cast substrates. Finally, fracture criteria from honeycomb model was used to estimate the maximum homogeneously distributed pressures, such as in fluids, that the substrates can withstand. This configuration represents more precisely practical conditions, though is hard to experimentaly replicate. Therefore, the developed procedure is paramount to simulate the mechanical behaviour of the tubular freeze-cast substrates under real operating conditions.

The synthesis of mesoporous materials in macroscopic scale, as for example, the monoliths, has been of great interest in view of the wide range of applications that this material holds. Thus, this work consists of the production of silica monoliths for the purpose of they being used in the carbon dioxide (CO2) adsorption process. The adsorbents were prepared in pure form and also with addition of heteroatoms: Al, Ti and Zr. The samples were then functionalized with pentaethylenehexamine (PEHA) by the wet impregnation method. The materials were characterized by the following techniques: X-ray diffraction (XRD), textural analysis, Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM) and Thermogravimetry (TG/DTG). The analyses indicated that the materials synthesized with heteroatom incorporation presented a disordered pore structure and high surface area (1387 m2/g for sample Ti/M1). In addition, they showed a significant increase in adsorption of CO2 relative to their parent sample, a fact that is not much explored in the literature. The CO2 adsorption performance tests were carried out at 30 ºC and atmospheric pressure. All functionalized materials demonstrated improved CO2 adsorption capacity relative to their starting samples. Adsorption capacities up to 111.3 mg/g were found in this work, which makes the materials developed promising candidates for the capture of CO2.

Development of new ceramic membranes has recently grown due to its superior thermal and mechanical stability. An interesting approach to manufacture asymmetric membranes is the production of aligned pore structure by the freeze-casting method. The lack of studies involving membrane production with tubular freeze-cast substrates warrants more research. In this study, a novel tubular freeze-cast alumina substrate was used for deposition of a silica top layer. The substrate showed radially aligned pores, indicating precise structure control. The obtained pore structure shows high potential for membrane manufacture. The silica layer was produced by the sol-gel method and dip-coated on the substrates with two different withdrawal speeds. The microporous silica showed pores smaller than 2 nm. The highest withdrawal speed resulted in broader substrate coverage. However, a uniform silica layer was only obtained after a second deposition. These results confirm the viability to use tubular freeze-cast substrates for production of nanofiltration membranes.

Abstract The use of geopolymer has been studied as a potential substitute for Portland cement due to lower CO2 emission and improvements on structural properties. Some of the major raw materials used in the manufacture of the geopolymer are: steel slag, fly ash and metakaolinite. Due to the impurities contained in these raw materials, the present study uses high purity synthetic aluminosilicates made from the sol gel process for production of geopolymers. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and nuclear magnetic resonance (NMR). The results showed that the synthetic aluminosilicates have similar behavior to metakaolinite (reference). It was found that the coordination of Al in the synthetic aluminosilicate changed from VI to IV and V from 300 °C, with the highest intensity at 900 °C. Temperature at which the highest mechanical strength of the geopolymer was also observed.

In the present report, Al-SBA mesoporous materials were investigated for use as water adsorbents. Different precursors for aluminum were investigated: aluminum sulfate and nitrate, boehmite, and aluminum tri-sec-butoxide. Furthermore, three different procedures for addition of the silica and alumina sources were tested. Samples were characterized by nitrogen adsorption to observe their textural characteristics and by thermogravimetric desorption of water to address their performance. The sample synthesized with aluminum tri-sec-butoxide as aluminum precursor and a pre-hydrolysis step of the silica source presented the highest adsorption capacity: 1057 g.kg-1. It was also observed that water attaches more strongly to Al-containing samples than to pure silica, and that water adsorption capacity is more related to the pore volume of samples than to their surface area. This work has shown that functionalizing SBA-15 materials with aluminum is a promising strategy for producing water adsorbents with improved performance and potential for many applications.

Mesoporous silica materials have been widely investigated for their great potential as competitive adsorbents and catalysts in different areas, due to their ordered and uniform porous structures and high surface area. In order to increase the availability of these materials, the need to granulate them becomes vital for an efficient performance in industrial units. This study reports the production and characterization of clay-free granules of SBA-15 mesoporous silica, by applying the extrusion technique. The suggested methodology uses only methocel as the organic binder, which is removed after calcination. The granulation process was successfully achieved, producing pure granules of SBA-15 mesoporous silica, in size of millimeters, with 8.3 MPa of compacting pressure (by axial crushing test). The surface area and pore volume of SBA-15 mesoporous silica granules (calcined at 800 ºC) were around 392 m2/g and 0.53 cm3/g, respectively.

Mineral rock wastes are being widely investigated due to possible damage to the environment when discarded indiscriminately in the nature, but also because of their great potential as ceramic raw materials. This work aims to study the effect of steatite particle additions on the mechanical properties of clay composites. A comprehensive series of experiments have been conducted to assess the influence of: steatite particle size, steatite fraction and compacting pressure on the performance of clay composites. The composite of superior properties was manufactured with 20 wt. (%) of steatite, 100-200 US-Tyler of steatite particle size and 30 MPa of compacting pressure.

The infrared bands of amethyst and prasiolite samples from different origins were correlated to the trace elements contents. Amethysts have an iron content greater than 20 ppm and a low content of sodium and potassium. Prasiolites have an aluminum content greater than 120 ppm and a higher overall trace elements content, which accounts for a strong absorption between 3200 and 3600 cm-1. Colorless samples of quartz that become amethysts and prasiolites after irradiation have infrared spectra at room temperature with a broad band at 3441 cm-1 and a sharp band at 3595 cm-1. The broad band splits in several bands at low temperatures that are related to AlSi and FeSi. The color of amethysts and prasiolites are assigned to [AlSiO4/h+]º and [FeSiO4/h+]º centers formed by the exposure to ionizing irradiation and to the influence of lattice distortions due to the content of iron as a substitute for silicon and a high content of trace elements of large ionic radius like potassium.

Adhesion between tiles and mortars are crucial to the stability of ceramic tile systems. From the chemical point of view, weak forces such as van der Waals forces and hydrophilic interactions are expected to be developed preferably at the tiles and polymer modified Portland cement mortar interface. The main goal of this paper was to use organosilanes as primers to modify ceramic tile hydrophilic properties to improve adhesion between ceramic tiles and polymer modified mortars. Glass tile surfaces were treated with several silane derivatives bearing specific functionalities. Contact angle measurements and Fourier Transform Infrared Spectroscopy (FTIR) were used for evaluating the chemical changes on the tile surface. In addition, pull-off tests were conducted to assess the effect on adhesion properties between tile and poly(ethylene-co-vinyl acetate), EVA, modified mortar. The bond strength results have clearly shown the improvement of adherence at the tile-polymer modified mortar interface, reflecting the overall balance of silane, cement and polymer interactions.

The aim of this study was to synthesize and characterize the biodegradable intraocular implants based on poly (D,L-lactide-co-glycolide) (PLGA 75:25) with Cyclosporine-A (CyA) and to evaluate their in vitro drug delivery profile. Thermal analysis was conducted by using Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). Phase analysis and crystallinity of the polymer-CyA samples were assessed through X ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Finally, microstructure and morphology of the systems were investigated by Scanning Electron Microscopy (SEM). The results showed that CyA was successfully incorporated into PLGA network with drug loading of approximately 31.6%. Also, based on FTIR and thermal analyses (TGA/DSC) no significant physical-chemical interaction was detected at the micro-nanoscale level between polymer/drug. SEM micrographs have indicated a uniform drug distribution in PLGA matrix. XRD patterns have showed that the incorporated semi-crystalline structure of CyA has not significantly altered the polymeric mainly amorphous network. In addition, the results have confirmed the chemical and biological drug stability, the drug distribution into the polymeric matrix and the possibility of cyclosporine prolonged delivery system profile.

Polyurethanes have been used in a series of applications due basically to their versatility in terms of controlling the behavior by altering basically the type of reagents used. However, for more specific and advanced applications, such as in membranes, biomaterials and sensors, well-organized and defined chemical functionalities are necessary. In this work, inorganic functionalities were incorporated into aliphatic polyurethanes (PU) having different macromolecular architectures. Polyurethanes were synthesized using a polyether diol and dicyclohexylmethane 4,4' diisocyanate (H12-MDI). Polyurethanes having carboxylic acid groups were also produced by introducing 2,2- bis (hydroxymethyl) propionic acid in the polymerization process. Inorganic functionalities were inserted into polyurethanes by reacting isocyanate end capped chains with aminopropyltriethoxysilane followed by tetraethoxysilane. PU having carboxylic acid groups yielded transparent samples after the incorporation of inorganic entities, as an evidence of smaller and better dispersed inorganic entities in the polymer network. FTIR and swelling measurements showed that polyurethanes having carboxylic acid groups had inorganic domains less packed, condensed and cross-linked when compared to polyurethanes with no carboxylic acid groups. Results also suggested that the progressive incorporation of inorganic moieties in both types of polyurethanes occurred in regions previously activated with inorganic functionalities, instead of by the creation of new domains. The temperatures of thermal decomposition and glass transition were also shifted to higher temperatures when inorganic functionalities were incorporated into polyurethanes.

Sol-gel film in the SiO2-CaO-P2O5 system was prepared from TEOS, TEP, alcohol and hydrated calcium nitrate in an acidic medium. The coatings were deposited on stainless steel using the dip-coating technique. After deposition, the composite was submitted to heat treatment, at different temperatures and exposure times to investigate the influence of such parameters on the surface morphology of the composite. The coated surfaces were characterized by AFM, SEM and FTIR. The present study showed that the formation of different textures (an important parameter in implant fixation) could be controlled by temperature and time of heat treatment.

This work describes the process for functionalization of laponite through the grafting of 3-mercaptopropyltrimethoxysilane (MPTS). Laponite is synthetic smectite clay with surface area of 350 m²/g. The samples, prior to and after functionalization, were characterized by chemical analyses, thermogravimetric analysis (TGA), x ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), scanning electron microscopy and energy dispersive spectrometry (MEV/EDS). Infrared spectroscopy and elemental analyses confirmed the presence of organic chains and thiol groups in the modified clay. The immobilized and available thiol group, measured according to the Volhard method, totaled 1.4 meq/g of clay, with approximately 90% accessible for Ag+ trapping. These results represent an improvement as compared to other works concerning the functionalization of smectite-type clays in which the effect produced by functional group blockage limits the access of species to less than 10% of the complexing sites.

Tissue engineering has evolved from the use of biomaterials for bone substitution that fulfill the clinical demands of biocompatibility, biodegradability, non-immunogeneity, structural strength and porosity. Porous scaffolds have been developed in many forms and materials, but few reached the need of adequate physical, biological and mechanical properties. In the present paper we report the preparation of hybrid porous polyvinyl alcohol (PVA)/bioactive glass through the sol-gel route, using partially and fully hydrolyzed polyvinyl alcohol, and perform structural characterization. Hybrids containing PVA and bioactive glass with composition 58SiO2-33CaO-9P2O5 were synthesized by foaming a mixture of polymer solution and bioactive glass sol-gel precursor solution. Sol-gel solution was prepared from mixing tetraethoxysilane (TEOS), triethylphosphate (TEP), and calcium chloride as chemical precursors. The hybrid composites obtained after aging and drying at low temperature were chemically and morphologically characterized through infrared spectroscopy and scanning electron microscopy. The degree of hydrolysis of PVA, concentration of PVA solution and different PVA-bioglass composition ratios affect the synthesis procedure. Synthesis parameters must be very well combined in order to allow foaming and gelation. The hybrid scaffolds obtained exhibited macroporous structure with pore size varying from 50 to 600 µm.